CN1070485C - Dithiazoldioxides and their use as microbiocidal agents - Google Patents

Abstract

The invention relates to novel dithiazoldioxides of general formula , in which R is hydrogen or optionally substituted alkyl, alkenyl or alkinyl, Ar is optionally substituted aryl, to a method for the production thereof and to the use thereof as technical materials for controlling microbial infestation.

Description

Dithiazole dioxide and its application as microbial control agent

The present invention relates to novel bithiazole dioxides, a process for their preparation and their use in crop protection and in material protection.

Dithiazole dioxides have been described, but their biological activity is not mentioned. (See, K. Dickoré, Lieb. Ann. Chem. 671, 135 (1964); US-PA3345374).

Surprisingly, it has now been found that the new compounds of general formula (I) are very suitable for protecting crops and materials

wherein R represents hydrogen or optionally substituted alkyl, alkenyl or alkynyl, and Ar represents optionally substituted aryl.

Formula (I) provides a general definition of the compounds of the invention. Preference is given to compounds of formula (I), wherein R represents hydrogen, a straight-chain or branched chain alkyl group with 1 to 10 carbon atoms, a straight-chain or branched chain alkenyl group with 2 to 10 carbon atoms or a group with 2 to 10 carbon atoms Straight-chain or branched alkynyl groups of 10 carbon atoms, which are optionally mono- to multi-substituted by identical or different substituents selected from the group consisting of: halogen, alkoxy having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms atom and 1 to 9 identical or different halogen atoms, haloalkoxy, alkylthio having 1 to 6 carbon atoms, haloalkylthio having 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, Acyl having 1 to 6 carbon atoms, acyloxy having 1 to 6 carbon atoms, (alkoxy)-carbonyl having 1 to 6 carbon atoms, optionally selected from the group consisting of alkyl and aryl or different substituents substituted amino, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano, and Ar represents aryl,

The aryl group is optionally mono-to-multiple substituted by substituents selected from the group consisting of halogen, alkyl having 1 to 10 carbon atoms, haloalkyl having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, Alkoxy having 1 to 10 carbon atoms, haloalkoxy having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkylthio having 1 to 10 carbon atoms, alkylthio having 1 to 8 3 carbon atoms and 1 to 8 identical or different halogen atoms, haloalkylthio, amino, straight-chain or branched chain alkyl groups having 1 to 6 carbon atoms, monoalkylamino, each having 1 to 6 carbons dialkylamino, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylene Dioxy, dichloromethylenedioxy, nitro or cyano.

Particularly preferred are compounds of formula (I), wherein R represents hydrogen, a straight-chain or branched chain alkyl group with 1 to 8 carbon atoms, a straight-chain or branched chain alkenyl group with 2 to 8 carbon atoms or a group with 2 Straight-chain or branched alkynyl groups of up to 8 carbon atoms, which are optionally mono- to tetrasubstituted by the same or different substituents selected from the group consisting of fluorine, chlorine, alkoxy having 1 to 5 carbon atoms, having 1 Haloalkoxy with 1 to 5 carbon atoms and 1 to 5 fluorine and/or chlorine atoms, alkylthio with 1 to 5 carbon atoms, 1 to 5 carbon atoms and 1 to 5 fluorine and/or chlorine atom haloalkylthio, acyl having 1 to 5 carbon atoms, acyloxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms, optionally selected from the group having 1 to 4 Alkyl of 2 carbon atoms and the same or different substituents of phenyl substituted amino, optionally substituted phenoxy, aryl, pyridyl, pyridyloxy, nitro or cyano, and Ar represents phenyl, The phenyl is optionally mono- to tetrasubstituted by the following substituents: fluorine, chlorine, alkyl having 1 to 8 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms , an alkoxy group having 1 to 8 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, an alkylthio group having 1 to 8 carbon atoms, a group having 1 Halogenated alkylthio groups of up to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, amino, monoalkylamino groups of alkyl groups having 1 to 4 carbon atoms, the same ones each having 1 to 4 carbon atoms or dialkylamino of different alkyl groups, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylene methylenedioxy, nitro or cyano.

Very particularly preferably, R represents hydrogen, methyl, ethyl, n- and i-propyl, n-, sec-, i- and tert-butyl, allyl and propargyl, which are optionally formed by fluorine and/or Chlorine, methoxy or methylthio substituted, and Ar represents phenyl, which is optionally mono- to trisubstituted by the following substituents: fluorine, chlorine, methyl, ethyl, n- and isopropyl, n-, sec -, iso- and tert-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano and/or phenoxy. Furthermore, it has now been found that compounds of formula (I) can be obtained by reacting a salt of general formula (II) with a diazonium salt of general formula (III) in aqueous/basic solution, if desired in the presence of a catalyst, wherein R is as defined above, and ^M represents an alkali metal or alkaline earth metal ion, in particular Na ⁺ , K ⁺ ,

Ar—N=N ^_ A ^_ (III) wherein Ar is as defined above, and A ^_ represents an anion of an inorganic acid.

Preferably, the solution of (II) is mixed with the base and, if desired, the catalyst, before mixing with the diazonium salt solution (III). Preferred bases are alkali metal hydroxides, such as potassium or sodium hydroxide. Suitable catalysts are all catalysts which promote the exchange of diazo functions for sulfur-containing groups.

Preference is given to using Cu(I) salts or copper powder. During the addition of the diazonium salt solution, the temperature can be varied within a wide range. Usually, the reaction is carried out at a temperature between -30°C and +60°C, preferably between -20°C and +40°C. The preparation of diazonium salt solutions from aniline is carried out by methods known from the literature.

Salts of general formula (II) can also be prepared by methods known from the literature (cf. references on page 1). The isolated salt of formula (II) can be used in solid form, or as a solution prepared in situ.

The active compounds according to the invention have a potent microbicidal action and can be employed for controlling harmful microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

In this context, the term "industrial material" is a non-living material that has been prepared for use in industry. Examples of industrial materials intended to be protected with the compounds of the invention from alteration or destruction by microorganisms are adhesives, sizes, paper and cards, fabrics, leather, wood, paints and plastics, cooling lubricants and materials subject to Other materials attacked and destroyed by microorganisms. With regard to the materials intended to be protected, mention may also be made of parts of productive plants, such as cooling water circuits, which can be adversely affected by the proliferation of microorganisms. In the context of the present invention, industrial materials that may be mentioned are preferably adhesives, sizes, paper and cards, textiles, leather, wood, paints, cooling lubricants and heat-conducting liquids.

Examples of microorganisms that can spoil or alter industrial materials are bacteria, fungi, yeasts, algae and slime mold microorganisms. Preferably, the active compounds according to the invention act preferably on bacteria, fungi, especially moulds, and on slime mold microorganisms and algae.

Microorganisms of the following genera may be mentioned by way of example:

Alternaria spp., such as Alternaria renuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Powdery mildew species such as Coniophora puteana,

Shiitake mushrooms, such as tiger skin mushroom (Lentinus tigrinus),

Penicillium, such as Penicillium glaucum,

Polyporus, Polyporus versicolor,

Aureobasidium pullulans, such as Aureobasidium pullulans,

Sclerophoma, such as S. pityophila,

Trichoderma, such as Trichoderma viride (rrichoderma viride),

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus spp., such as Staphylococcus aureus.

The fungicidal compositions in crop protection are used for the control of the Plazodiomycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Some of the pathogenic fungal diseases listed above are given by generic name, the following may be mentioned, for example, but by no means limited thereto:

Pythium, such as Pythium ultimum;

Phytophthora, such as Phytophthora infestans;

Pseudoperonospora, such as Pseudoperonospora humuli or P. cubensis;

Plasmopara viticola, such as Plasmopara viticola;

Peronospora, such as Peronospora pisi or P. brassicae;

Erysiphe graminis, such as Erysiphe graminis;

Sphaerotheca fuliginea, such as Sphaerotheca fuliginea;

Podococci, such as Podosphaera leucotricha;

Venturia inaequalis, such as Venturia inaequalis;

Pyrenophora teres, such as Pyrenophora teres or P. graminea (conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus sativus, such as Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);

Monospore rusts, such as Uromyces appendiculatus;

Puccinia recondita, such as Puccinia recondita;

Tilletia spp., such as Tilletia caries;

Ustilago species such as Ustilago nuda or U. avenae;

Thinfilmella spp., such as Pellicularia sasakii;

Pyricularia spp., such as Pyricularia oryzae;

Fusarium spp., such as Fusarium culmorum;

Botrytis, such as Botrytis cinerea;

Septoria, such as Septoria nodorum;

Leptosphaeria nodorum, such as Leptosphaeria nodorum;

Cercospora, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae, and

Pseudomicrocercospora, such as Pseudocercosporalla herpotrichoides.

The good crop safety of the active compounds according to the invention at the concentrations required for the control of plant diseases makes it possible to treat aerial parts of plants, vegetative stocks and seeds as well as the soil.

Depending on their specific physical and/or chemical properties, the active compounds can be converted into customary dosage forms such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulated polymers.

These formulations can be produced in known manner, for example, by mixing the active compounds with extenders (i.e. liquid solvents, pressurized liquefied gases) and/or with solid carriers, optionally using surfactants (i.e. emulsifiers). and/or dispersants and/or foaming agents). In the case of water as the filler, organic solvents can also be used as co-solvents. As liquid solvents, suitable mainly are: aromatic compounds, such as xylene, toluene or alkylnaphthalene, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorinated benzenes, vinyl chloride or methylene chloride, aliphatic hydrocarbons , such as cyclohexane or paraffins, e.g. mineral oil fractions, alcohols such as butanol or ethylene glycol and their ethers and esters, ketones such as acetone, ethyl ketone, methyl isobutyl ketone or cyclohexanone, Strong polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water; liquefied gas fillers or carriers are liquids that are gases at ambient temperature and atmospheric pressure, such as aerosol propellants, such as butane, propane , nitrogen and carbon dioxide; solid carriers are suitable: ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as Dispersion of silica, alumina and silicates; suitable solid carriers for granules are, for example, crushed and broken natural minerals such as calcite, marble, pumice, sepiolite and dolomite, and organic and inorganic powders Synthetic granules of synthetic granules, and granules of the following organic substances: sawdust, coconut shells, corn cobs and tobacco stems; emulsifiers and/or foaming agents are suitable: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters , polyoxyethylene fatty alcohol ethers, for example, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates; suitable dispersants are: for example, wood elemental sulfurous acid waste liquid and methyl cellulose.

In formulations, binders such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and egg Phospholipids, and synthetic phospholipids. Other binders may be mineral and vegetable oils.

It is also possible to use dyes, such as inorganic pigments, such as iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and micronutrients such as iron, manganese, boron, copper, cobalt , molybdenum and zinc salts.

The potency and activity spectrum (if desired) of the active compounds of formula (I) and of the compositions, precursors or general preparations which can be prepared therefrom can be determined by adding another antimicrobial compound, fungicide, bactericide, herbicide, Insecticides or other active compounds, thereby broadening the spectrum of activity or obtaining special effects such as additional protection against insect infestation. These mixtures will have a broader spectrum of activity than the compounds of the invention.

In many cases, a synergistic effect is obtained, ie the activity of the mixture is greater than that of the individual components. Particularly suitable components thereof are, for example, the following compounds: triazoles, such as

Herbicide, triazoltin, BAS 480F, bisbenzotriazole, oxaconazole, fenbuconazole, oxaconazole, fenethanil, fluquinconazole, flusilazole, fluquinazole, amide azole, isozofos, mycloconazole, metconazole, Epoxyconazole, paclobutrazol, penconazole, propiconazole, (±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl )-Cycloheptanol, fluteconazole, triadimefon, triadimenol, imabazole, fluconazole, triticonazole, uniconazole and their metal salts and acid additions. imidazoles, such as

Imazalil, Blasticate, Prochloraz, Fluconazole, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazole-1- base)-propan-2-ol, thiazolecarboxyl (N-phenyl)amines such as 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl -1,3-thiazole-5-carboxyl(N-phenyl)amine, 1-imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, and Its metal salts and acid adducts.

(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2 -[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2-[6-(2 -fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2-[6-(2,6-difluorophenoxy) Pyrimidin-4-yloxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]- Methyl 3-methoxyacrylate, (E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxymethylacrylate , (E)-2-[2-[3-(phenylsulfonyloxy)phenoxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2-[3- Methyl (4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, (E)-2-[2-phenoxyphenyl]-3-methoxymethylacrylate , (E)-2-[2-(3,5-dimethylbenzoyl)pyrrol-1-yl]-3-methoxymethyl acrylate, (E)-2-[2-(3- Methoxyphenoxy)phenyl]-3-methoxyacrylate methyl ester, (E)-2-[2-(2-styrene-1-yl)phenyl]-3-methoxymethoxymethacrylate ester, (E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxymethyl acrylate, (E)-2-(2-(3- (1,1,2,2-Tetrafluoroethoxy)phenoxy)phenyl)-3-methoxymethyl acrylate, (E)-2-(2-[3-(α-hydroxybenzyl )phenoxy]phenyl)-3-methoxymethyl acrylate, (E)-2-[2-(4-phenoxypyridin-2-yloxy)phenyl]-3-methoxy Methyl acrylate, (E)-2-[2-(3-n-propoxyphenoxy)phenyl]-3-methoxymethyl acrylate, (E)-2-[2-(3-iso Propoxyphenoxy)phenyl]-3-methoxymethyl acrylate, (E)-2-[2-(3-(2-fluorophenoxy)phenoxy)phenyl]-3- Methyl methoxyacrylate, (E)-2-[2-(3-ethoxyphenoxy)phenyl]-3-methoxymethylacrylate, (E)-2-[2-(4 -Methyl tert-butylpyridin-2-yloxy)phenyl]-3-methoxyacrylate, (E)-2-[2-[3-(3-cyanophenoxy)phenoxy] Phenyl]-3-methoxymethyl acrylate, (E)-2-[2-(3-methylpyridin-2-yloxymethyl)phenyl]-3-methoxymethyl acrylate, (E)-2-[2-[6-(2-methylphenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxymethyl acrylate, (E)-2-[2 -(5-bromopyridin-2-yloxymethyl)phenyl]-3-methoxymethyl acrylate, (E)-2-[2-(3-(3-iodopyridin-2-yloxy Base) phenoxy) phenyl] -3-methoxymethyl acrylate, (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy ]phenyl]-3-methoxymethyl acrylate, (E),(E)-2-[2-(5,6-dimethylpyrazin-2-ylmethoxyiminomethyl)phenyl ]-3-methoxymethyl acrylate, (E)-2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3- Methyl methoxyacrylate, (E), (E)-2-{2-(3-methoxyphenyl)methyloximinomethyl]phenyl}-3-methoxymethylacrylate, ( E)-methyl 2-{2-[6-(2-azidophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, (E),(E)- Methyl 2-{2-[6-phenylpyrimidin-4-ylmethyloximinomethyl]phenyl}-3-methoxyacrylate, (E), (E)-2-{2-[( 4-Chlorophenyl)methyloximinomethyl]phenyl}-3-methoxymethylacrylate, (E)-2-{2-[6-(2-n-propylphenoxy)-1 ,3,5-triazin-4-yloxy]phenyl}-3-methoxymethyl acrylate, (E),(E)-2-{2-[(3-nitrophenyl)methyl methyl oximinomethyl]phenyl}-3-methoxyacrylate; succinate dehydrogenation inhibitors such as

Tofuranilide, Dimethofuranilide, Cyclohexamid, Seedvax, Seedvax, Thiamid, Pyrocarbolid, Oxietrazin, Antimycodamine, Rustamine, Ortho-iodanilide, Fluoramide;

Naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-yne );

Sulfonamides, such as fenflusulfonamide, tolueneflusulfonamide, folpet, fluorfolpet; captan, captafol;

Benzimidazoles, such as carbendazim, benomyl, furocarb, thiocarbamate, thiocarbazine, thiabendazole and their salts;

Morpholine derivatives, such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidin and their aromatic sulfonic acids, such as p-toluenesulfonic acid and p-dodecanoic acid Alkylphenylsulfonic acid;

Dithiocarbamate, such as dyson salt, thiram, mancocopper, mancozeb, maneb, webamu, thiram, thiram, zinc, thiram;

Benzothiazoles, such as 2-mercaptobenzothiazole;

Benzamides, such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;

Boron compounds such as boric acid, borate esters, borax;

Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono(poly)hemiformal, oxazoline, hexahydro-s-triazines, N-methyl alcohol chloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid, Kuphthalene;

Tris-N-(cyclohexyldiazeniumdioxyl)-aluminum, N-(cyclohexyldiazeniumdioxyl)-tributyltin or potassium salt, bis-N-(cyclohexyldiazenium dioxy) Oxygen)-copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl Baseisothiazolin-3-one, 4,5-trimethylene-isothiazolinone, 4,5-benzisothiazolinone, N-methylalcohol chloroacetamide;

Aldehydes, such as lauric aldehyde, formaldehyde, glutaraldehyde, β-bromolauric aldehyde;

Thiocyanates, such as thiocyanomethylthiobenzothiazole, methylene dithiocyanate, etc.;

Quaternary ammonium compounds, such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;

Iodine derivatives, such as diiodomethyl-p-tolylsulfone, 3-iodo-2-propynol, 4-chloro-phenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo -2-propenylethyl carbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propyne N-butyl carbamate, 3-iodo-2-propynyl n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propargyl Phenyl carbamate;

Phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali metal and alkaline earth metal salts;

Microbicides with activated halogen groups, such as chloroacetamide, bronopol, bronidox, tectamer, such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetyl Benzene, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;

Pyridines, such as 1-hydroxy-2-pyridinethione (and its sodium, iron, manganese and zinc salts), tetrachloro-4-methylsulfonylpyridine, pyridinemethanol, azoxycarbin, pyridil, 1- Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridine;

Metallic soaps such as tin naphthenate, copper naphthenate, zinc naphthenate, tin octoate, copper octoate, zinc octoate, tin 2-ethylhexanoate, copper 2-ethylhexanoate, 2-ethylhexanoate Zinc, Tin Oleate, Copper Oleate, Zinc Oleate, Tin Phosphate, Copper Phosphate, Zinc Phosphate, Tin Benzoate, Copper Benzoate, and Zinc Benzoate;

Metal salts, such as basic copper carbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

Oxides, such as tributyltin oxide, cuprous oxide, copper oxide, zinc oxide;

Dialkyldithiocarbamates, such as sodium and zinc dialkyldithiocarbamates, tetramethylthiuram dioxide, N-methyl-dithiocarbamic acid Ester potassium salt;

Nitriles, such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyanodithioimidazolyl carbamate;

Quinolines, such as 8-hydroxyquinoline and its copper salt;

Mucchloric acid, 5-hydroxy-2(5H)-furanone;

4,5-dichlorobithiazolone, 4,5-benzobithiazolone, 4,5-trimethylenebithiazolone, 4,5-dichloro-(3H)-1,2-di Thiol-3-one, 3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexyl chloride Ammonium, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate,

2-oxo-2-(4-hydroxy-phenyl)hydroxamic acid chloride,

Phenyl 2-chloro-cyano-vinylsulfone,

Phenyl 1,2-dichloro-2-cyano-vinylsulfone;

Zeolites containing silver, zinc or copper, either alone or encapsulated in polymeric active compounds.

Very particularly preferred mixtures are those with the following active ingredients:

Teconazole, Fuconazole, Cycloconazole, Benconazole, Diniconazole, Hexaconazole, Metaconazole, Penconazole, Propiconazole, Tebuconazole, (E)-Methoxyimino[ α-(o-tolyloxy)-o-tolyl]]acetic acid methyl ester, (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl }-3-Methoxymethyl acrylate, pyraclostrobin, wiltapine, seed dressing, 4-(2,2-difluoro-1,3-benzodioxolan-4-yl)-1H -pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octyl Isothiazolin-3-one, benzisothiazolinones, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)formal, glutaraldehyde, milidine, dimethyl dicarbonate ester and/or 3-iodo-2-propynyl n-butylcarbamate.

Furthermore, highly active mixtures can also be prepared with the following active ingredients: Fungicides:

acypetacs, 2-aminobutane, amalinate, difenazol, benalaxyl, pyrimethrimol sulfonate, mimetimeng, dimaosan, aceclozolin, cymoxanil, dacemuron, pyridoxine, Clonitramine, Dimethocarb, Pyromethanol, Diocab, Dithianon, Dodine, Hydrazolone, Kewensan, Pyrimol, Terendazim, Chlorphenidol, Seedcoating, Triphenyltin acetate, triphenyltin hydroxide, pyrizazone, fluazinam, chlorfenapyril, sulfanil, fuconazole, phosphonium, tetrachlorophthalide, furaxyl, grain seeds Ding, hymexazol, isofendazine, iprodione, riceblastyl, metalaxyl, sulfocarb, isopropyl m-nitrophthalene, fluoropyrimidol, tofuramide, oxaxyl, perflurazoate, pentamethylene Bacterilon, Rice Phosphorus, Pimaricin, Biaohualing, Procymidone, Propionamide, Procyonium, Pyriphos, Pyrifos, Pyroquinone, Pentachloronitrobenzene, Tar, Tetrachloronitrate Base benzene, thiabendonil, thiocarbazone-methyl, likuling-methyl, pyraclostrobin, salicilamide, tricyclazole, pyrinamin, vinclozolin. Insecticides:

Phosphate esters, such as cottonphos, acetophos, α-(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxypyrazole, chlorpyrifos, acetophos, endogenous Phosphate, Demeton-methyl, Diazinon, Dichlorvos, Dimethoate, Yiguo, Methion, Phyrifos, Fenitrothion, Fenthion, Heptenphos, Parathion, Methylpara Thion, thion, phoxim, pirimiphos, pirimiphos-methyl, profenofos, prothion, methion, triazophos and trichlorfon;

Carbamates, such as aldicarb, bentoxacarb, α-2-(1-methylpropyl) phenylmethyl carbamate, butanonecarb, butanoneoxycarb, carbaryl, gramper Carbosulfan, Carbosulfan, Chuxiancarb, Yechansan, Methomyl, Shaxiancarb, Pimicarb, Manshacarb, Proxacarb and Thiodicarb;

Organosilicon compound, preferably dimethyl(phenyl)silyl-methyl 3-phenoxybenzyl ether, such as dimethyl(4-ethoxyphenyl)silyl-methyl 3-phenoxy benzyl ether, or (dimethylphenyl)silyl-methyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl-(9-ethoxyphenyl)silane yl-methyl-2-phenoxy-6-pyridylmethyl ether, or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silane, such as [(4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)-propyl](dimethyl)-silane, Xerox (silafluofen);

Pyrethroids such as allethrin, alpha-cypermethrin, bioresmethrin, bifenthrin, cypermethrin, cyfluthrin, deltamethrin, cyhalothrin, cypermethrin, Deltamethrin, α-cyano-3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate , fenpropathrin, penfluthrin, fenvalerate, flucyvalerate, bifenthrin, fluvalinate, permethrin, resmethrin, and deltamethrin;

Nitroimino and nitromethylene compounds such as 1-[(6-chloro-3-pyridyl)-methyl-4,5-dihydro-N-nitro-1H-imidazol-2-amine (imidacloprid ), N-[(6-chloro-3-pyridyl)methyl-]N2-cyano-N1-methylacetamide (NI-25);

Abamectin, AC303630, acephate, fluatethrin, acetaminocarb, oxyaldicarb, aldrin, acetamiprid, methyl pyroxaphos, Bacillus thuringiensis, imothion, phosphorus Amines, phosphine, ketonethrin, profenfos, fenprofen, fagus, pyrazophos, pyrethrins, pyridaben, pyridazinphos, pyriproxyfen, quetiafos, RH-7988 , Tripenone, Sodium Fluoride, Sodium Hexafluorosilicate, Phosphate, Methylsulfonyl Fluoride, Tar, Fufenuron, Tefluthrin, Teflufos, Terbufos, Insecticide, Aminothrin Esters, O-2-tert-butylpyrimidin-5-yl-o-isopropyl-phosphorothioate, dimecyclam, monotocarb, methionon, tetrabromothrin, triflumeron, mixed meth Carbocarb, Aphidol, Verticillium lactis, Mechucarb, Meoxacarb, Carbosulfan, Bisulphon, Bifenthrin, Bio-allethrin, MER Bio-allethrin, (S)- Cyclopentenyl isomers, bromthiofos, ethylbromthiofos, buprofezin, methimen, calcium polysulfide, trithion, cartap, acarid, chlordane, chlordane, chlordane Chlorpyrifos, chlormethion, chloropicrin, chlorpyrifos, fenitrophos, cyfluthrin, alpha-cypermethrin, phenetrin, cyromazine, dacetron, DDT, sulfone, fensulfuron, imine chloride Thionphos, dicrotophos, diflubenzuron, dimethol, deoxabenzofos, daizacarb, dinitrophos, dinitrophenol, ethynethrin, endosulfan, fenthion, esfenvalerate, ethylthiobencarb, Ethion, Ethoproxil, Bubucarb, Fenoxycarb, Nematophos, Fipronil, Flufenuron, Flufenprox, Flubenzuron, Tefenthion, Fentamiprid , Anguo, fenfenfos, furosecarb, heptachlor, fluorinated urea, hydrazone, hydrogen cyanide, methoprene, fenprofos, chlorazophos, isopropylamidophos, rice blast, Azophos, iodophos, thiathrin, lindane, malathion, aphids, dianphos, calomel, Anbaimu, Metarthizium anisopliae, carnivora, methamidophos, methaphos, methamidophos Suocarb, methoprene, methoxychlor, dimethoate, medicarb, sulfolafos, monocrotophos, dibromophos, Neodiprion sertifer NPV, nicotine, omethoate, sulfoxide, pentachlorophenol , Petroleum, Phenothrin, Daofengsan, Phorate; Molluscicide:

Triphenyltin acetate, snail enemy, methoxacarb, conch snail, thiodicarb, and mixicarb. Algicide:

Copper Sulfate, Dichlorophen, Indozad, Triphenyltin Acetate, Cycloquinone. herbicide:

Acetochlor, acifluorfen, acenifen, acrolein, alachlor, mopropion, ametryn, amidosulfuron, acetap, ammonium sulfamate, sapon, sulphon, atraz Zijin, azide, grass-killing, butadiflunid, furoxan, bensulfuron, diazanphos, bentazone, buzazodone, benzhiuron, carboxyben, bialanylphos , Borax, 2,4-Dipropionic Acid, Homo-2,4-Dipropionic Acid, Diclopyr, Acemethachlor, Cucuron, Dibendazole, Diflufenamide, Dioxachloron, Diphenhydramine , dimetolachlor, dimethyrethylamine, thimethine, cacodylic acid, aminoefluridine, diphenol, diphenoxyacetate, webacidine, bromobutyramid, pronitrophenol, Bromoxynil, butachlor, imazafos, fuenachlor, proprachlorin, butachlorate, carzachlor, CGA184927, methoxyfen, methazapine, lvxiulong, barnyard Polygonum, positive form, herbicide Mineral, chlorimuron, aquat, chloroacetic acid, chloropicrin, chlorotoluron, subtilon, chlorphenamine, chlorsulfuron, chlorphthalic acid, grass gram, cycloheptafen, ether sulfuron, Clethodim, Clomazone, Barnyard, Clopyralid, Calcium Chloride, Cyanazine, Dimethol Acetate, Terofen, Dibenzamide, Propylene, Diquat , Dithiopyr, Diuron, Dinitrophenol, PPX-A788, DPX-E 96361, Metharsinic acid, Ganpujing, Indoza, Indalim, Difenba, Ethylfluridine, Saihuanglong, ethyl furazone, oxaprop-ethyl, high oxaprop-methyl, feuron, wheat straw, wheat straw M, pyrisulfuron, pyriflora-prop, high-pyrazoxaprop , ciproflurane, fluorumuron, fluroxyfen-ethylcarboxylate, fluoroben, tetrafluoropropionic acid, fluorenbutyric acid, fluoridinone, fluroxypyrone, fluroxypyr, methazide, cycloxydone , 2,4-D, Diuron, Maturon, Methonon, 2,4-D Butyric Acid, Betaine, Diquat, Dicamba, Dichronil, Isoproturon, Isocolon, Clomazone Amines, oxafefen, lactofen, cyclopyridine, rituron, sulfafos, 2-methyl-4-chloro, 2-methyl-4-chlorothioethyl, 2-methyl-4-chlorobutyric acid, 2-methyl-4-chloroprop Acid, high 2-methyl-4-chloropropionic acid, mefenacet, voltachlor, metabam, methoxazone, metazachlor, methylbenthiazole, methazol, methoxypropane, methylherbicide Long, Dimensinate, Xiugulong, Fxanthamfen, Vifenfos, Furofen, Glufosin-ammonium, Glyphosate, Haloxyfop, Hexazinone, Imazethapyr, Imazapyr, Imazethapyr, imazethapyr, ioxynil, propramid, pentynchlor, benzalt, pyrazolate, pyrazosulfuron, benzamazole, barnyard grass, pyridate, dichloroquinoline Acid, algae quinone, quizalofop, quizalofop, S-23121, sethoxydim, cyclosulfuron, simazine, simazine, SMY 1500, sodium chlorate, rimsulfuron, tar, triclosan Acetic acid, metolachlor, methoxuron, metrixazone, mesulfuron, turfone, heptazolid, lvgulong, methylarsinic acid, naproxenamine, naphthalam, turfron, nicotin Huanglong, diclofenac, pyridoxine, pingcaodan, ansulfone, oxadiazone, ethoxyfluorfen, paraquat, gram grass, methylamine cysulfuron, pentachlorophenol, valerophenone Grass ammonium, petroleum, beetinin, picloram, diphenafos, pretilachlor, chlorimuron, aminoproflurazine, glycyrrhizin, prometone, permeant, toxachlor, formosan, terbuthiauron, Terbutydine, terdingtong, terbutyzine, terbutene, thiafluron, grass-killer, zhongcaodan, pyrimazamid, sammazone, wild swallow fear, ether benzsulfuron, benzosulfuron, trichlopyr , Metracycline, Cadazine, Trifluralin, IBI-C4874, Mezameda, Propannil, Oxachlorate, Promethazine, Anilinine.

The weight ratios of the active compounds in these active compound combinations can be varied within relatively wide ranges.

The active compound combination preferably contains from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, of the active compounds according to the invention, the remainder being one or more of the above-mentioned co-components, rounded up to 100%. .

The microbicidal compositions or concentrates for the protection of industrial materials comprise the present active compounds or the present active compound combinations in concentrations of 0.01 to 95% by weight, in particular 0.1 to 60% by weight.

The intended application concentration of the active compound or the active compound combination depends on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum application rate can be determined by a series of experiments. The use concentration is usually in the range of 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the material to be protected.

The active compounds or compositions according to the invention advantageously allow the replacement of existing microbicidal compositions by more effective and less toxic compositions. They have good stability and (preferably) a broad spectrum of activity.

The following examples illustrate the invention. The present invention is not limited to these examples. Preparation Example Example 2

5 g (26 mmol) of 1,4,2-dithiazole-3-thiol 1,1-dioxide potassium salt was dissolved in 13 mL of 20% KOH, mixed with 1.82 g of Cu powder, and Cool to about 0°C to 5°C. During 30 minutes, the diazonium salt solution (I) was added dropwise, and the reaction mixture was allowed to warm to room temperature and filtered off with suction. The filter cake was washed with water and then treated with ethyl acetate. The mixture was filtered again, and the filtrate was washed twice with 2N HCl. The mixture was dried over sodium sulfate, concentrated and chromatographed on silica gel (toluene/ethyl acetate=10:1).

To remove colored impurities, the product was stirred with a little diisopropyl ether and filtered off with suction.

Yield: 2.9 g (39% of Δth.) as light gray powder, mp=172°C.

Diazonium salt solution (I):

At 2°C, first add 3.31 g (26 mmol) of 4-chloroaniline to 46 ml of water and 6.5 ml of concentrated hydrochloric acid, then add 1.9 g of NaNO ₂ in 15.6 ml of aqueous solution dropwise for mixing, and stir the mixture for another 1 hour .

Compounds of formula (I) listed in Table 1 were also prepared analogously to this example and according to the general procedure above.

应用实施例ATable 1 (Dithiazole Dioxide I)

Application Example A

For evaluating antifungal activity, the minimum inhibitory concentration (MIC) of the composition of the present invention is determined:

Agar prepared using malt extract is mixed with the active compound of the present invention at a concentration of 0.1 mg/l to 5,000 mg/l. When the agar had solidified, it was infected with pure cultures of the test organisms listed in Table 2. The samples were stored for 2 weeks at 28° C. and 60 to 70% relative air humidity, after which the MIC was determined. The MIC is the lowest concentration of active compound at which no colonies of the species of microorganisms used occur and is listed in Table 2 below.

实施例B：The minimum inhibitory concentration (ppm) of formula (I) compound of the present invention of table 2 Example serial number 2 3 4 Comparative compound* Penicillium aureus <40 <40 <40 400 Chaetomium globosa <40 <40 <40 400 Aspergillus niger <40 <40 <40 >400 *From US3,345,374, Example 27 on page 2

Example B:

Experiment on Protective Control of Tomato Late Blight

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the stated amounts of solvent and emulsifier, and the emulsifiable concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until moistened with dew. After the spray coating has dried on, the plants are inoculated with a conidia suspension of the fungus Phytophthora infestans.

The plants are placed in an incubation room at 100% relative humidity and approximately 20°C.

Evaluations were performed 3 days after inoculation.

At an active compound concentration of 100 ppm, Preparation Example 5 showed an efficacy of 90%. Example C:

Experiment on protective control of grape downy mildew

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the stated amounts of solvent and emulsifier, and the emulsifiable concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until moistened with dew. After the spray coating has dried on, the plants are inoculated with a conidia suspension of the fungus Plasmoparaviticola. Plants were placed in a humidity chamber at 100% relative humidity and 20-22°C. The plants are then left for 5 days at 21° C. and an air humidity of approximately 90%. Afterwards, the plants were hydrated and placed in a humidity chamber for 1 day.

Evaluations were performed 6 days after inoculation.

At an active compound concentration of 100 ppm, preparation examples 1, 5 and 6 exhibit an efficacy of greater than 73%. Example D:

Experiment on Protective Control of Soybean Botrytis Cinerea

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To prepare a suitable formulation of the active compound, 1 part by weight of the active compound is mixed with the stated amounts of solvent and emulsifier, and the emulsifiable concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until moistened with dew. After the spray coat had dried, 2 small pieces of agar with Botrytis cinerea colonies were placed on each leaf. The inoculated plants were placed in a dark humidity chamber at 20°C. Three days after inoculation, the size of the infected spots on the leaves was evaluated.

At an active compound concentration of 500 ppm, preparation examples 1, 2, 5, 6 and 14 exhibit an efficacy of greater than 80%.

Claims (6)

1. A compound of general formula (I), wherein R represents hydrogen, methyl, ethyl, n- or isopropyl, n-, sec-, iso- and tert-butyl, allyl and propargyl, optionally consisting of fluorine and/or chlorine, methoxy Substituted by radical or methylthio, and Ar represents phenyl, which is optionally mono- to trisubstituted by the following substituents: chlorine, fluorine, methyl, ethyl, n- and isopropyl, n-, sec-, iso- and tert-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano and/or phenoxy. 2. Microbicidal compositions, characterized in that they comprise at least one compound of formula (I) according to claim 1 . 3. A method for controlling microorganisms, characterized in that the compounds of the formula (I) according to claim 1 are allowed to act on the microorganisms and/or their habitat. 4. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that In aqueous/alkaline solution, if necessary in the presence of a catalyst, the salt of general formula (III) is reacted with the diazonium salt of general formula (III), in R is as defined in claim 1, and M ^_ represents an alkali metal or alkaline earth metal ion, especially Na ⁺ , K ⁺ , Ar-N=N ^_ A ^_ (Ⅲ) wherein Ar is as defined in claim 1, and A ^_ represents an anion of an inorganic acid. 5. Use of the compound of formula (I) according to claim 1 for controlling microorganisms. 6. Use of compounds of formula (I) according to claim 1 for the protection of industrial materials against attack by microorganisms.